CN110371943A - A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste - Google Patents
A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of nickle cobalt lithium manganates and LiFePO4 mixing waste selective recovery technique, comprising the following steps: dry, pulverize nickle cobalt lithium manganate and LiFePO4 mixing waste, is sieved, obtains mixed powder；Mixed powder is added in acid solution, transforming agent, acidleach processing are added, filtering respectively obtains ferrophosphorus kish slag and nickel and cobalt containing manganese ferrophosphorus lithium filtrate；Precipitating reagent and transforming agent are added in nickel and cobalt containing manganese ferrophosphorus lithium filtrate, pH is adjusted, filtering respectively obtains phosphoric acid scum and nickel and cobalt containing manganese lithium filtrate；The pH of nickel and cobalt containing manganese lithium filtrate is adjusted, filtering respectively obtains nickel cobalt manganese slag and filtrate containing lithium, washes, dries to nickel cobalt manganese pulp water, obtains nickel cobalt manganese carbonate or hydroxide；Sodium phosphate is added in filtrate containing lithium, lithium is mentioned, filters, respectively obtains liquid and lithium phosphate after sinker.The present invention can LiFePO4 waste material to nickel and cobalt containing manganese carry out selective recovery, for lithium leaching rate up to 99%, nickel, manganese leaching rate are more than 95%.
Description
Technical field
The invention belongs to lithium ion battery material recovery technology fields, and in particular to a kind of nickle cobalt lithium manganate and LiFePO4
The selective recovery technique of mixing waste.
Background technique
LiFePO4 (LiFePO4) stable structure, has extended cycle life, environmentally friendly, abundant raw material, cheap, quilt
It is largely used to the positive electrode active materials of lithium ion battery.Over time, it is using the electric car of ferric phosphate lithium cell
Extensive disenabling stage will be entered, it is contemplated that by 2021, there will be the ferric phosphate lithium cell of more than 9000 tons to enter disenabling stage.It is waste and old
Ferric phosphate lithium cell much all joined the valuable metals such as nickel, cobalt and manganese and be doped modification, will if do not handled it
Serious pollution is caused to environment.
That reports at present has following several method: (1) patent of invention about LiFePO4 waste material treatment process
CN106340692B (a method of the lithium in positive electrode is recycled in cleaning) LiFePO4 waste material, weak base and water are blended in two
Be separated by solid-liquid separation after being reacted under carbonoxide, heating condition, obtain mentioning evaporation-after lithium liquid be separated by solid-liquid separation-be drying to obtain carbon
Sour lithium product, but the lithium rate of recovery is not high in waste material.(2) patent of invention CN 109193059A (a kind of regeneration of LiFePO4 waste material
Treating method) by after the progress constituent analysis of LiFePO4 waste material, it carries out separating-composition adjustment-ferrous phosphate presoma processed-phosphorus processed
Sour lithium presoma-mixed slurry-system processed uncoated LiFePO4-cladding and sintering, Direct Regeneration obtain iron phosphate lithium positive pole
Material, but due to containing aluminium in raw material, and removal of impurities processing is not carried out, it may contain in regenerated lithium iron phosphate positive material
Impurity is to influence the performance of material.(3) patent of invention CN108483418A (a kind of LiFePO4 waste material treatment process) is used
Electric discharge-broken apart-alkali soluble obtains battery-grade iron phosphate except aluminium-sulfuric acid leaching-phosphoric acid sinks iron, and filtrate is collected-adjust pH value-
Adding Urea reaction-filtering-filter residue that water slurry-is added to be passed through carbon dioxide reaction to pH is 9, obtains battery-level lithium carbonate.The party
Method realizes the recycling of phosphorus, iron, lithium, and obtained product purity is higher, but complex technical process, complex steps, and is difficult to reach
To higher leaching rate.The LiFePO4 waste material handled in report at present is the pure ferric phosphate lithium waste material not being doped mostly,
And rarely handle the report of the mixing waste of nickel and cobalt containing manganese impurity.
Therefore, it is mixed to need to develop a kind of technical process is simple, recycling product purity is high nickle cobalt lithium manganate and LiFePO4
Close the selective recovery technique of waste material.
Summary of the invention
The purpose of the present invention is to provide the selective recovery technique of a kind of nickle cobalt lithium manganate and LiFePO4 mixing waste,
The technical process is simple, recycling product purity, to pollute small, at low cost and economic benefit higher.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste, comprising the following steps:
(1) nickle cobalt lithium manganate and LiFePO4 mixing waste dry, pulverize, is sieved, obtains nickle cobalt lithium manganate and phosphoric acid
Iron lithium mixed powder；
(2) it takes nickle cobalt lithium manganate and LiFePO4 mixed powder to pour into acid solution, adds transforming agent, carry out at acidleach
Reason, filtering, respectively obtains ferrophosphorus kish slag and nickel and cobalt containing manganese ferrophosphorus lithium filtrate；
(3) precipitating reagent and transforming agent are added in nickel and cobalt containing manganese ferrophosphorus lithium filtrate, and it is 3- that alkaline material, which is added, to adjust pH
5, filtering respectively obtains phosphoric acid scum and nickel and cobalt containing manganese lithium filtrate；
(4) pH of nickel and cobalt containing manganese lithium filtrate is adjusted to 9-12, filters, respectively obtains and wash nickel cobalt manganese slag and filtrate containing lithium,
It washed, dried to washing nickel cobalt manganese slag again, obtain nickel cobalt manganese carbonate or hydroxide；
(5) sodium phosphate is added in filtrate containing lithium, carries out mentioning lithium, filtered, respectively obtain liquid and lithium phosphate after sinker.
Preferably, in step (1), the drying is that nickle cobalt lithium manganate and LiFePO4 mixing waste is dry to water content
≤ 1.0wt%.
Preferably, in step (2), the acid solution is selected from one or both of sulfuric acid and hydrochloric acid.
Preferably, in step (2), the H of the acid solution+Dosage is 1.2-6.2 times of lithium mole in raw material, acid used
H+Concentration is 0.5-4mol/L, and the mass ratio of the acid solution and mixed powder is 3-10:1.
Preferably, in step (2), the acidleach processing carries out at 30 DEG C -90 DEG C, and the time is 1-5 hours.
Preferably, in step (2), the transforming agent is selected from hydrogen peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate, perchloric acid
One or more of sodium and hypochlorous acid.
Preferably, in step (2), the mole that the transforming agent is added is 0.1-1.5 times of lithium mole in raw material.
Preferably, in step (2), the transforming agent is added in the form being added dropwise, and the time of dropwise addition is 0-45min.
Preferably, in step (3), the precipitating reagent is one of ferrous sulfate, frerrous chloride, iron chloride and ferric sulfate
Or it is a variety of.
Preferably, in step (3), the dosage of the precipitating reagent is 1.0-3.0 times of the mole of phosphorus in solution；Described turn
The dosage of agent is 1.0-5.0 times that precipitating reagent mole is added；The temperature that precipitating reagent is added is 60 DEG C -80 DEG C.
Preferably, in step (3), the alkaline material is one in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide
Kind is several.
Preferably, in step (5), the dosage of the sodium phosphate is 1.0-5.0 times of lithium mole in solution.
Preferably, in step (5), the lithium that mentions carries out at 70 DEG C -95 DEG C, time 1-5h.
The method have the benefit that:
(1) technique of the invention can LiFePO4 waste material to nickel and cobalt containing manganese carry out selective recovery, lithium leaching rate is reachable
99% or more, nickel, manganese leaching rate are more than 95%, and cobalt leaching rate is more than 92%, and phosphorus leaching rate is less than less than 2%, iron leaching rate
0.5%, it can reach the selective recovery of valuable metal.
(2) present invention process process is simple, easy to operate, and pollution is small, and lower to equipment requirement, value of the product is higher, warp
It helps profitable.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by embodiment, to the present invention into
Row is further described.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
In limiting the scope of the invention.
Embodiment 1
A kind of nickle cobalt lithium manganate and LiFePO4 mixing waste selective recovery technique, comprising the following steps:
(1) nickle cobalt lithium manganate and LiFePO4 mixing waste is dry to water content≤1.0wt%, it crushes, sieving obtains
Nickle cobalt lithium manganate and LiFePO4 mixed powder；
(2) 62.74g (0.628mol, 1.25 times of lithium mole in raw material) concentrated sulfuric acid is weighed to pour under stiring
In 593.6mL water, it is configured to the sulfuric acid solution of 1mol/L；
(3) it weighs 120.0g nickle cobalt lithium manganate and LiFePO4 mixed powder pours into step (2) in prepared sulfuric acid,
The beaker for installing material is placed in 85 DEG C of water-baths, and opens stirring, acid and material liquid-solid ratio are 6.277:1 in this reaction；
(4) 57.12g (in raw material 1.0 times of lithium mole) 30% hydrogenperoxide steam generator is weighed, with dropper slowly by peroxide
Change hydrogen to instill in (3) described reaction system, be dripped off in 30min, the calculating reacting time since being added dropwise hydrogen peroxide, is reacted
4h obtains material；
(5) material filtering that will be obtained after step (4) reaction, filtrate are the leachate of nickeliferous, cobalt, manganese, lithium, contain part
Phosphorus, iron tramp, volume 572.0mL, filter residue are the mixing leached mud of acidleach insoluble matter and ferric phosphate in raw material, quality 99.6g；
(6) leachate is taken to measure nickel, cobalt, manganese, lithium, phosphorus, iron content, after leached mud is washed 5 times, drying is accurately weighed
Leached mud after 1.00g drying, with chloroazotic acid (HCl:HNO3=3:1) molten slag, it is settled to 250mL, is measured in molten slag liquid after filtering
Phosphorus, iron, nickel, cobalt, manganese, lithium content and calculate leaching rate；
(7) leachate is added with stirring 2.276g (in solution 2.0 times of phosphorus mole) green vitriol at 80 DEG C
Solid, and 0.872g sodium chlorate (1 times that ferrous mole is added) is added, and adjust pH to 4.0, filtering with sodium hydroxide solution
Except dephosphorization, iron tramp, filtrate continuously adds sodium hydroxide solution and adjusts pH to 12, filtering, and filter residue is nickel cobalt manganese hydroxide, water
81.93g sodium phosphate (the 1.0 of lithium mole in solution are added in dry, quality 19.70g after washing, filtrate under the conditions of 90 DEG C
Times), after reacting 4h, lithium phosphate product is filtered to obtain, quality is 24.50g after drying.
Each ingredient calculated result such as the following table 1 in embodiment 1:
Each ingredient calculated result in table 1- embodiment 1
Embodiment 2
A kind of nickle cobalt lithium manganate and LiFePO4 mixing waste selective recovery technique, comprising the following steps:
(1) nickle cobalt lithium manganate and LiFePO4 mixing waste is dry to water content≤1.0wt%, it crushes, sieving obtains
Nickle cobalt lithium manganate and LiFePO4 mixed powder；
(2) 136.27g (1.387mol, 3 times of lithium mole in raw material) concentrated hydrochloric acid is weighed to pour into 577.03mL water, match
The hydrochloric acid solution of 2mol/L is made；
(3) it weighs 100g nickle cobalt lithium manganate and LiFePO4 mixed powder pours into prepared hydrochloric acid, material will be installed
Beaker be placed in 75 DEG C of water-baths, and open stirring, acid and material liquid-solid ratio are 6.935:1 in this reaction；
(4) 41.92g (in raw material 0.8 times of lithium mole) 30% hydrogenperoxide steam generator is weighed, with dropper slowly by peroxide
Change hydrogen to instill in the reaction system of step (3), be dripped off in 30min, the calculating reacting time since being added dropwise hydrogen peroxide, is reacted
3h obtains material；
(5) step (4) are reacted to obtained material filtering, filtrate is the leaching of nickeliferous, cobalt, manganese, lithium and part phosphorus, iron
Liquid, volume 550.0mL, filter residue are the mixing leached mud of acidleach insoluble matter and ferric phosphate in raw material, quality 82.2g；
(6) it takes leachate to measure nickel, cobalt, manganese, lithium, phosphorus, iron content to accurately weigh after leached mud is dried after washing 5 times
1.00g is settled to 250mL with chloroazotic acid (HCl:HNO3=3:1) molten slag, after filtering measure molten slag liquid in phosphorus, iron, nickel, cobalt,
Manganese, lithium content simultaneously calculate leaching rate；
(7) it is solid to be added with stirring 5.70g (in solution 5 times of phosphorus mole) green vitriol at 75 DEG C for leachate
Body, and the sodium chlorate solid of 1.75g (0.8 times that ferrous ion mole is added) is added, and adjust pH with sodium hydroxide solution
To 4.0, it is filtered to remove phosphorus, iron tramp, filtrate is added sodium hydroxide solution and adjusts pH to 12, filtering, and filter residue is nickel cobalt manganese hydrogen-oxygen
Compound, after washing, slag amount is 14.46g, and 75.14g sodium phosphate (lithium mole in solution is added in filtrate under the conditions of 95 DEG C
1.0 times), after reacting 3h, sodium phosphate product is filtered to obtain, quality is 17.70g after drying.
Each ingredient calculated result such as the following table 2 in embodiment 2:
Each ingredient calculated result in table 2- embodiment 2
Embodiment 3
A kind of nickle cobalt lithium manganate and LiFePO4 mixing waste selective recovery technique, comprising the following steps:
(1) nickle cobalt lithium manganate and LiFePO4 mixing waste is dry to water content≤1.0wt%, it crushes, sieving obtains
Nickle cobalt lithium manganate and LiFePO4 mixed powder；
(2) 31.4g (0.314mol, 1.15 times of lithium mole in raw material) concentrated sulfuric acid is weighed to pour into 296.7mL water, match
The sulfuric acid solution of 1mol/L is made；
(3) it weighs 60g nickle cobalt lithium manganate and LiFePO4 mixed powder pours into prepared sulfuric acid, and material will be installed
Beaker be placed in 90 DEG C of water-baths, and open stirring, acid and material liquid-solid ratio are 5.23:1 in this reaction；
(4) 18.42g (in raw material 0.6 times of lithium mole) 30% hydrogenperoxide steam generator is weighed, with dropper slowly by peroxide
Change hydrogen to instill in the reaction system of step (3), be dripped off in 30min, the calculating reacting time since being added dropwise hydrogen peroxide, is reacted
5h；
(5) step (4) reaction is obtained into material filtering, filtrate is nickeliferous, cobalt, manganese, lithium and and the leaching of phosphorus, iron on a small quantity
Liquid, volume 285.0mL, filter residue are the mixing leached mud of insoluble matter and ferric phosphate in raw material, quality 51.7g；
(6) leachate is taken to measure nickel, cobalt, manganese, lithium, phosphorus, iron content, leached mud is washed 5 times, after drying, 1.00g is weighed,
With chloroazotic acid (HCl:HNO3=3:1) molten slag, it is settled to 250mL, phosphorus, iron, nickel, cobalt, manganese, the lithium measured in slag solution after filtering contains
It measures and calculates leaching rate；
(7) leachate is added with stirring 0.736g (in solution 1.5 times of phosphorus mole) green vitriol at 60 DEG C
Solid, and 20mL30% hydrogen peroxide is added, and adjust pH to 4.5 with sodium hydroxide solution, it is filtered to remove phosphorus, iron tramp, mistake
After filter, filtrate is added sodium carbonate liquor and adjusts pH to 9-10, filtering, and filter residue is nickel cobalt manganese carbonate products, repeatedly after washing, slag
Quality is 12.10g, measure filtrate in nickel, cobalt, manganese content and calculate rate of deposition, 44.56g is added under the conditions of 85 DEG C in filtrate
Sodium phosphate (in solution 1 times of lithium mole) filters to obtain sodium phosphate product after reacting 5h, and quality is 10.60g after drying.
Each ingredient calculated result such as the following table 3 in embodiment 3:
Each ingredient calculated result in table 3- embodiment 3
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. the selective recovery technique of a kind of nickle cobalt lithium manganate and LiFePO4 mixing waste, which is characterized in that including following step
It is rapid:
(1) nickle cobalt lithium manganate and LiFePO4 mixing waste dry, pulverize, is sieved, obtains nickle cobalt lithium manganate and LiFePO4
Mixed powder；
(2) nickle cobalt lithium manganate and LiFePO4 mixed powder are added in acid solution, add transforming agent, carry out acidleach processing,
Filtering, respectively obtains ferrophosphorus kish slag and nickel and cobalt containing manganese ferrophosphorus lithium filtrate；
(3) precipitating reagent and transforming agent are added in nickel and cobalt containing manganese ferrophosphorus lithium filtrate, alkaline material is added and adjusts pH value to 3-5, mistake
Filter, respectively obtains phosphoric acid scum and nickel and cobalt containing manganese lithium filtrate；
(4) pH value of nickel and cobalt containing manganese lithium filtrate is adjusted to 9-12, filters, respectively obtains nickel cobalt manganese slag and filtrate containing lithium, then right
Nickel cobalt manganese slag is washed, is dried, and nickel cobalt manganese carbonate or hydroxide are obtained；
(5) sodium phosphate is added in filtrate containing lithium, carries out mentioning lithium, filtered, respectively obtain liquid and lithium phosphate after sinker.
2. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (1), the drying is that nickle cobalt lithium manganate and LiFePO4 mixing waste is dry to water content≤1.0wt%.
3. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (2), the acid solution is selected from one or both of sulfuric acid and hydrochloric acid.
4. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 or 3 and LiFePO4 mixing waste, special
Sign is, in step (2), H in the acid solution+Amount be the H of acid used 1.2-6.2 times of lithium mole in raw material+Concentration
For 0.5-4mol/L, the mass ratio of the acid solution and mixed powder is 3-10:1.
5. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 or 3 and LiFePO4 mixing waste, special
Sign is, in step (2), the acidleach processing carries out at 30 DEG C -90 DEG C, and the time is 1-5 hours.
6. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (3), the transforming agent is selected from hydrogen peroxide, sodium chlorate, sodium hypochlorite, potassium chlorate, sodium perchlorate and hypochlorous acid
One or more of；The precipitating reagent is one of ferrous sulfate, frerrous chloride, iron chloride and ferric sulfate or a variety of.
7. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (2), the dosage of the transforming agent is 0.1-1.5 times of lithium mole in raw material.
8. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (3), the dosage of the precipitating reagent is 1.0-3.0 times of the mole of phosphorus in solution；The dosage of the transforming agent
For 1.0-5.0 times that precipitating reagent mole is added；The temperature that precipitating reagent is added is 60 DEG C -80 DEG C.
9. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (5), the dosage of the sodium phosphate is 1.0-5.0 times of lithium mole in filtrate containing lithium.
10. the selective recovery technique of nickle cobalt lithium manganate according to claim 1 and LiFePO4 mixing waste, feature
It is, in step (5), the lithium that mentions carries out at 70 DEG C -95 DEG C, time 1-5h.
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| CN110760686A (en) * | 2019-12-13 | 2020-02-07 | 九江天赐高新材料有限公司 | Method for recovering lithium from waste lithium ion battery |
| CN112342383A (en) * | 2020-09-17 | 2021-02-09 | 湖北金泉新材料有限公司 | Method for separating and recovering nickel, cobalt, manganese and lithium in ternary waste |
| CN113809424A (en) * | 2021-08-25 | 2021-12-17 | 广东邦普循环科技有限公司 | Method for recycling mixed waste of lithium nickel cobalt manganese oxide and lithium iron phosphate |
| CN114597399A (en) * | 2022-02-15 | 2022-06-07 | 广东邦普循环科技有限公司 | Preparation method and application of vanadium iron sodium phosphate material |
| CN115321502A (en) * | 2022-08-01 | 2022-11-11 | 广西埃索凯循环科技有限公司 | Comprehensive recovery process for waste lithium iron phosphate battery and nickel-cobalt-manganese ternary battery |
| CN115367725A (en) * | 2022-08-29 | 2022-11-22 | 广东邦普循环科技有限公司 | Doped lithium iron phosphate and preparation method and application thereof |
| CN116581413A (en) * | 2023-05-22 | 2023-08-11 | 甘肃睿思科新材料有限公司 | Method for jointly recovering lithium, cobalt, iron and phosphorus from waste lithium iron phosphate and waste lithium cobaltate |
| CN116902999A (en) * | 2023-05-31 | 2023-10-20 | 广东盛祥新材料科技有限公司 | Ternary powder/lithium iron powder/lithium carbonate processing method and waste battery recycling method |
| CN116947118A (en) * | 2023-07-14 | 2023-10-27 | 埃索凯循环能源科技(广西)有限公司 | Method for preparing nickel-manganese-iron ternary precursor and iron phosphate by recycling waste batteries |
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